JP2010209238A - Vinyl chloride-based resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vinyl chloride-based resin composition excellent in weatherability. <P>SOLUTION: The vinyl chloride-based resin composition contains, in 100 pts.mass of a vinyl chloride-based resin, (a) 0.001-10 pts.mass of at least one of a hindered amine compound represented by general formula (I) and another specific hindered amine compound and (b) 0.001-10 pts.mass of at least one selected from the group consisting of a metal salt of perchloric acid and the like. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a vinyl chloride resin composition, and more particularly, to a vinyl chloride resin composition having excellent weather resistance and heat aging resistance by combining a hindered amine compound having a specific carbonate skeleton and perchlorates. .

  Vinyl chloride resins such as vinyl chloride resins are excellent in flame retardancy and chemical resistance, and are used in various applications such as building materials, agricultural and industrial equipment materials, and automotive parts. However, the vinyl chloride resin has the disadvantage that it is thermally decomposed to cause dehydrochlorination, resulting in a decrease in mechanical strength and coloration, thereby impairing commercial properties.

  In order to solve the above-described drawbacks, various stabilizers have been developed, and it is known that lead compounds, cadmium compounds and barium compounds, and the like have particularly excellent stabilizing effects. However, in recent years, the use of lead compounds and cadmium compounds has been restricted from the viewpoint of safety, and high safety zinc compounds and alkaline earth metal organic acid salts, hydrotalcite, inorganic compounds such as zeolites, etc. It is being changed to stabilization by combined use.

  However, these low-toxicity stabilizers cannot provide a sufficient stabilizing effect by themselves, so organic phosphite compounds, epoxy compounds, phenolic antioxidants, UV absorbers such as benzophenone or benzotriazole, hindered amines, etc. Various additives for improving the resistance against light, heat, oxidation, etc., such as a system light stabilizer, are used in combination.

  Patent Document 1 proposes a low basic hindered amine compound having a carbonate skeleton.

International Publication No. 2005/082852

  However, a higher degree of weather resistance has been required for the vinyl chloride resin composition, such as when used for a sheet for automobiles. Moreover, even when the hindered amine compound described in Patent Document 1 is added alone to the vinyl chloride resin, there is room for improvement.

  Accordingly, an object of the present invention is to provide a vinyl chloride resin composition having excellent weather resistance.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by using a combination of a hindered amine compound having a specific carbonate skeleton and perchlorates, The present invention has been completed.

（式中、Ｒは炭素原子数１〜３０のアルキル基もしくはヒドロキシアルキル基、または炭素原子数２〜３０のアルケニル基を、ｎは１〜６の整数を表し、ｎ＝１のときＲ^１は炭素原子数１〜２２のアルキル基、炭素原子数２〜２２のアルケニル基または下記一般式（ＩＩＩ）、

（Ｒは上記Ｒと同じ炭素原子数１〜３０のアルキル基もしくはヒドロキシアルキル基、又は炭素原子数２〜３０のアルケニル基を表す）の基を表し、ｎ＝２〜６のときＲ^１はｎ価の炭素原子数２〜２０の有機基を表す）
または下記一般式（ＩＩ）、

（式中、Ｒは炭素原子数１〜３０のアルキル基もしくはヒドロキシアルキル基、または炭素原子数２〜３０のアルケニル基を表し、Ｒ^２は水素原子、炭素原子数１〜２２のアルキル基又は炭素原子数２〜２２のアルケニル基を表し、Ａは単結合、炭素原子数１〜１２の直鎖もしくは分岐のアルキレン基、またはエーテル結合を有するアルキレン基を表し、ｎは２〜６の整数を表し、Ｘは−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）Ｏ−を末端に有する炭素原子数４〜４０の直鎖もしくは分岐のアルキレン基、−Ｃ（＝Ｏ）Ｏ−を末端に有し、途中にエーテル結合を有する炭素原子数４〜４０の直鎖もしくは分岐のアルキレン基、炭酸エステル結合を有する炭素原子数４〜４０の直鎖もしくは分岐のアルキレン基、または３〜６個の−Ｏ−Ｃ（＝Ｏ）−を末端に有する炭素原子数６〜３０の有機基を表す）で表されるヒンダードアミン化合物の少なくとも一種を０．００１〜１０質量部と、
（ｂ）過塩素酸の金属塩、過塩素酸のアンモニウム塩、過塩素酸処理ハイドロタルサイトおよび過塩素酸処理珪酸塩からなる群から選ばれる少なくとも一種を０．００１〜１０質量部と、を含有することを特徴とするものである。 That is, the vinyl chloride resin composition of the present invention comprises (a) the following general formula (I),

(In the formula, R represents an alkyl or hydroxyalkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, n represents an integer of 1 to 6, and when n = 1, R ¹ is An alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or the following general formula (III),

(R represents the same alkyl group having 1 to 30 carbon atoms or hydroxyalkyl group as that of R, or an alkenyl group having 2 to 30 carbon atoms), and when n = 2 to 6, R ¹ is n Represents an organic group having 2 to 20 carbon atoms)
Or the following general formula (II),

(In the formula, R represents an alkyl group having 1 to 30 carbon atoms or a hydroxyalkyl group, or an alkenyl group having 2 to 30 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or carbon. Represents an alkenyl group having 2 to 22 atoms, A represents a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or an alkylene group having an ether bond, and n represents an integer of 2 to 6 , X is a linear or branched alkylene group having 4 to 40 carbon atoms having —C (═O) — or —C (═O) O— as a terminal, and having —C (═O) O— as a terminal. And a linear or branched alkylene group having 4 to 40 carbon atoms having an ether bond, a linear or branched alkylene group having 4 to 40 carbon atoms having a carbonic ester bond, or 3 to 6- O-C (= O)-end 0.001 to 10 parts by mass of at least one kind of hindered amine compound represented by an organic group having 6 to 30 carbon atoms at the end)
(B) 0.001 to 10 parts by mass of at least one selected from the group consisting of metal salts of perchloric acid, ammonium salts of perchloric acid, perchloric acid-treated hydrotalcite and perchloric acid-treated silicate, It is characterized by containing.

In the general formula (I), the vinyl chloride resin composition of the present invention is such that R is an alkyl group having 4 to 22 carbon atoms, n is 2, and R ¹ is an alkylene group having 2 to 12 carbon atoms. It is preferable.

Furthermore, in the vinyl chloride resin composition of the present invention, in the general formula (I), n is 1 and R ¹ is a group of the general formula (III) (wherein R is an alkyl group having 10 to 22 carbon atoms). It is preferable that

  Furthermore, the vinyl chloride resin composition of the present invention is preferably used for powder molding and is preferably used for automobile seats.

According to the present invention, it is possible to provide a vinyl chloride resin composition that is excellent in weather resistance and heat aging resistance and can be suitably used as an automobile sheet.

  Hereinafter, the vinyl chloride resin composition of the present invention (hereinafter also referred to as “composition”) will be described in detail.

  The vinyl chloride resin used in the present invention is not particularly limited to the polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. For example, polyvinyl chloride, chlorinated polyvinyl chloride, polychlorination Vinylene, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride- Vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile solution, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride -Chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-male Vinyl chloride resins such as acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-various vinyl ether copolymers, and their blends or other chlorines Synthetic resins not containing acrylonitrile, such as acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer, blended product with polyester, etc. Examples thereof include a block copolymer and a graft copolymer.

  The hindered amine compound which is the component (a) of the present invention is a hindered amine compound having a carbonate skeleton and represented by the above general formula (I) or (II).

  Examples of the alkyl group having 1 to 30 carbon atoms represented by R in the general formulas (I) and (II) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, Linear or branched such as dipentyl, tertiary pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl And cycloalkyl groups such as a cyclohexyl group.

  Examples of the hydroxyalkyl group having 1 to 30 carbon atoms represented by R in the general formulas (I) and (II) include 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-2-methylpropyl Etc.

  The R may be the same or different for every n units.

  Examples of the alkenyl group having 2 to 30 carbon atoms represented by R in the general formulas (I) and (II) include alkenyl groups corresponding to the alkyl groups such as vinyl, allyl, butenyl, pentenyl, oleyl and the like.

In the general formula (I), when n = 1, R ¹ represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or the general formula (III).

In the general formula (I), when n = 1, the alkyl group having 1 to 22 carbon atoms represented by R ¹ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl , Pentyl, secondary pentyl, tertiary pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, behenyl Etc.

In the general formula (I), examples of the alkenyl group having 2 to 22 carbon atoms represented by R ¹ when n = 1 include alkenyl groups corresponding to the above alkyl groups such as vinyl, allyl, butenyl, pentenyl, oleyl, and the like. Can be mentioned.

In the general formula (I), when n = 1, when R ¹ represents a group of the general formula (III), R in the general formula (III) is the same as R in the general formula (I). Although they are mentioned, they may be the same as or different from R in the general formula (I). R is preferably an alkyl group having 10 to 22 carbon atoms.

In the above general formula (I), when n = 2 to 6, the n-valent organic group having 2 to 20 carbon atoms represented by R ¹ includes an alkylene group and the like, as well as hydroxy of an n-valent polyvalent hydroxy compound. Examples thereof include a residue excluding a group.

  Examples of the polyvalent hydroxy compound include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6- Hexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, hydrogenated product of bisphenol A, hydrogenated product of bisphenol F, diethylene glycol, triethylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. Is mentioned.

In the general formula (II), R ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms.

Examples of the alkyl group having 1 to 22 carbon atoms represented by R ² include those having the corresponding number of carbon atoms among the alkyl groups in R.

In the general formula (II), examples of the alkenyl group having ² to 22 carbon atoms represented by R ² include those having the corresponding number of carbon atoms among the alkenyl groups in R. The R ² may be the same or different for every n units.

  In the general formula (II), A represents a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or an alkylene group having an ether bond.

  Examples of the alkylene group include methylene, 1,2-ethylene, 1,2-propylene, 1,3-propylene, tetramethylene, 1,2-butylene, 1,3-butylene, pentamethylene, 2,2- Examples include dimethyltrimethylene, hexamethylene, and octamethylene.

Examples of the linear or branched alkylene group having 1 to 12 carbon atoms and having an ether bond represented by A in the general formula (II) include:
_{-CH 2 CH 2 -O-CH 2} CH 2 -,
_{-CH 2 CH (CH 3) -O} -CH 2 CH (CH 3) -,
_{-CH 2 CH 2 -O-CH 2} CH 2 -O-CH 2 CH 2 -
Etc.

  A may be the same or different for each of n units (n is 2 to 6).

  In the above general formula (II), X represents —C (═O) —, or represents a linear or branched alkylene group having 4 to 40 carbon atoms having —C (═O) O— at its end, It represents a linear or branched alkylene group having 4 to 40 carbon atoms having —C (═O) O— at the end and having an ether bond in the middle, or having 4 to 40 carbon atoms having a carbonate ester bond. It represents a linear or branched alkylene group, or represents an organic group having 6 to 30 carbon atoms having 3 to 6 —O—C (═O) — at its terminal.

As the alkylene group having 4 to 40 carbon atoms having a —C (═O) —O— bond represented by X in the general formula (II) as an end,
_{-C (= O) -O- (CH} 2) p -O-C (= O) -
(P is a number from 2 to 40)
Etc.

As the alkylene group having a carbonate ester bond represented by X in the general formula (II),
—C (═O) —R ³ —O—C (═O) —O—R ³ —C (═O) —
(R ³ represents an alkylene group having 2 to 18 carbon atoms.)
Etc.

Moreover, the following group etc. are mentioned as an organic group which has 3-6 -O-C (= O)-which X represents in the said general formula (II) at the terminal.

  More specifically, examples of the compound represented by the general formula (I) include compound Nos. 1-No. 6 and compound no. 13 compounds, and examples of the compound represented by the general formula (II) include Compound No. 7-No. 12 compounds are mentioned. However, the present invention is not limited by the following compounds.

Compound No. 1

Compound No. 2

Compound No. 3

Compound No. 4

Compound No. 5

Compound No. 6

Compound No. 7

Compound No. 8

Compound No. 9

Compound No. 10

Compound No. 11

Compound No. 12

Compound No. 13

  Content of the said (a) component is 0.001-10 mass parts with respect to 100 mass parts of vinyl chloride-type resin, Preferably it is 0.01-5 mass parts, In the use below 0.001 mass part, The added effect may not be sufficiently exhibited, and if it is used in excess of 10 parts by mass, there is a possibility that large coloring may occur, such being undesirable.

  The component (b) used in the present invention is at least one selected from the group consisting of a perchloric acid metal salt, an ammonium perchlorate salt, a perchloric acid-treated hydrotalcite, and a perchloric acid-treated silicate.

  Examples of the metal constituting the perchloric acid metal salt include lithium, sodium, potassium, calcium, magnesium, strontium, barium, zinc, cadmium, lead, and aluminum. The perchloric acid metal salt may be an anhydride or a hydrated salt, and may be one dissolved in an alcohol or ester solvent such as butyl diglycol or butyl diglycol adipate or a dehydrate thereof.

  The ammonium perchlorate salt may be an anhydrous salt or a hydrated salt.

  The perchloric acid-treated hydrotalcite is a perchloric acid-modified product in which part or all of the carbonic acid of the hydrotalcite compound is replaced with perchloric acid.

The hydrotalcite compound is a carbonic acid double salt compound of magnesium and / or zinc and aluminum, and is preferably a compound represented by the following general formula (IV).
Mg _x1 Zn _x2 Al ₂ (OH) _{2 (X1 + X2) + 4} · CO ₃ · mH ₂ O (IV)
(In the formula, x1 and x2 each represent a number that satisfies the condition represented by the following formula, and m represents a real number. 0 ≦ x2 / x1 <10, 2 ≦ x1 + x2 <20)

  The hydrotalcite compound may be a natural product or a synthetic product. Examples of methods for synthesizing the above synthetic products include known methods described in Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. Sho 61-174270, and the like. can do. In the present invention, the hydrotalcite compound can be used without being limited by the crystal structure, the crystal particle system, the presence or absence of crystal water and the amount thereof.

  The perchloric acid-treated hydrotalcite has a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic sulfonic acid metal salt such as an alkali metal dodecylbenzenesulfonate, Those coated with fatty acid amides, higher fatty acid esters or waxes can also be used.

  The perchloric acid-treated hydrotalcite can be easily produced, for example, by adding hydrotalcite to a dilute aqueous solution of perchloric acid and stirring, followed by filtration, dehydration or drying as necessary. . In this case, the molar ratio between the hydrotalcite and the perchloric acid can be arbitrarily set. Generally, the molar ratio of perchloric acid is 0.1 to 2 moles with respect to 1 mole of hydrotalcite. It is preferable to use it.

  As the above-mentioned perchloric acid-treated silicate, silicate metal salts such as calcium silicate, magnesium silicate, barium silicate, zinc silicate and various siliceous clay minerals or treated products thereof, for example, kaolin, bentonite, mica powder, talc, diatomaceous earth, Examples include those obtained by treating natural or synthetic silicates such as acid clay, activated clay and zeolite with an aqueous perchloric acid solution. Among these perchloric acid-treated silicates, calcium silicate, magnesium silicate, barium silicate, kaolin Bentonite, talc, acid clay, activated clay, and processed zeolite are preferred.

  The perchloric acid-treated silicate can be easily produced, for example, by adding silicate to a dilute aqueous solution of perchloric acid and stirring, followed by filtration, dehydration or drying as necessary. Although the molar ratio of the silicate and perchloric acid can be arbitrarily set, it is generally used at a ratio of 0.1 to 2 mol of perchloric acid with respect to 1 mol of silicate. Is preferred.

  Content of the said (b) component is 0.001-10 mass parts with respect to 100 mass parts of vinyl chloride-type resin, Preferably it is 0.01-5 mass parts, More preferably, it is 0.05-3 mass parts. . If the content is less than 0.001 part by mass, the effect is hardly seen, and if it exceeds 10 parts by mass, the effect is not increased, but rather the heat resistance, colorability and the like may be adversely affected.

  In the vinyl chloride resin composition of the present invention, plasticizers usually used for vinyl chloride resins can be used. Examples of the plasticizer include dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, Phthalate plasticizers such as dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate; adipate plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, di (butyldiglycol) adipate; triphenyl Phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, tri Phosphate plasticizer systems such as octyl phosphate, tri (butoxyethyl) phosphate octyl diphenyl phosphate; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3 -Butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol, etc. and dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelin Polyester plasticizer using acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc., and if necessary monohydric alcohol or monocarboxylic acid as a stopper; Acid plasticizer, pyromellitic acid plasticizer, tetrahydrophthalic acid plasticizer, azelaic acid plasticizer, sebacic acid plasticizer, stearic acid plasticizer, citric acid plasticizer, biphenyltetracarboxylic acid ester A plasticizer, a chlorine plasticizer, etc. are mentioned.

  The content of the plasticizer is determined as needed, but is usually 0 to 200 parts by mass, particularly 10 to 80 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

  Further, the composition of the present invention includes other additives usually used in vinyl chloride resin compositions, such as metal salts of organic carboxylic acids, phenols and organic phosphoric acids, zeolite compounds, hydrotalcite compounds, β -Diketone compounds, epoxy compounds, polyhydric alcohols, phenol-based, phosphorus-based and sulfur-based antioxidants, UV absorbers, hindered amine-based light stabilizers, and other inorganic metal compounds can be added.

  Examples of the metal constituting the metal salts of the organic carboxylic acids, phenols, and organic phosphoric acids include lithium, potassium, sodium, calcium, magnesium, barium, aluminum, and zinc.

  Examples of the organic carboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, neodecanoic acid, capric acid, undecanoic acid, lauric acid, Tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5 -Di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N, N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid , P-tertiary octylsalicylic acid, elaidic acid, oleic acid Monovalent carboxylic acids such as linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, octyl mercaptopropionic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebatin Divalent carboxylic acids such as acid, phthalic acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, thiodipropionic acid Or a monoester or monoamide compound thereof; a di- or triester compound of a trivalent or tetravalent carboxylic acid such as butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, merophanic acid, or pyromellitic acid. It is.

  Examples of the phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, isooctylphenol, 2 -Ethylhexylphenol, tertiary nonylphenol, decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisofuxylphenol, methyl tertiary octylphenol and the like.

  Examples of the organic phosphoric acids include mono or dioctyl phosphoric acid, mono or didodecyl phosphoric acid, mono or dioctadecyl phosphoric acid, mono or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, and phosphonic acid stearyl ester. Mono or dioctyl phosphorous acid, mono or dioctadecyl phosphorous acid, and the like.

  In addition, the metal salts of the above organic carboxylic acids, phenols, and organic phosphoric acids are acidic, neutral salts, basic salts, or overbased complexes obtained by neutralizing a part or all of basic salt bases with carbonic acid. It may be.

  The zeolite compound is an aluminosilicate of an alkali or alkaline earth metal having a unique three-dimensional zeolite crystal structure, and typical examples thereof include A-type, X-type, Y-type and P-type zeolite, monodenite, anal Sites, sodalite group aluminosilicates, clinobutyrolite, erionite and chabazite, etc., and water-containing substances having crystal water (so-called zeolite water) of these zeolite compounds or anhydrides from which crystal water has been removed In addition, those having a particle size of 0.1 to 50 μm can be used, and those having a particle size of 0.5 to 10 μm are particularly preferable.

  Further, the hydrotalcite compound is a carbonate double salt compound of magnesium and aluminum detailed in the column of perchloric acid-treated hydrotalcite, preferably a compound represented by the above general formula (IV) is there.

  In addition, the hydrotalcite compound has a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic sulfonic acid metal salt such as an alkali metal dodecylbenzenesulfonate, a higher fatty acid amide, Those coated with higher fatty acid esters or waxes can also be used.

  Examples of the β-diketone compound include dehydroacetic acid, dibenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, and the like, and these metal salts are also useful.

  Examples of the epoxy compound include bisphenol type and novolak type epoxy resins, epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, and epoxidized safflower oil. , Epoxidized tall oil fatty acid octyl, epoxidized linseed oil fatty acid butyl, epoxy methyl stearate, -butyl, -2-ethylhexyl or -stearyl, tris (epoxypropyl) isocyanurate, 3- (2-xenoxy) -1,2 -Epoxypropane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxyl Rate, bis (3,4-epoxycyclohexyl) adipate, and the like.

  Examples of the polyhydric alcohol include pentaerythritol, dipentaerythritol, sorbitol, mannitol, trimethylolpropane, ditrimethylolpropane, pentaerythritol or dipentaerythritol stearic acid partial ester, bis (dipentaerythritol) adipate, Examples include glycerin, diglycerin, and tris (2-hydroxyethyl) isocyanurate.

  Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris ( Mono-, di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) -ethyl phosphite, diphenyl acid phosphite, 2,2'-methylene bis (4,6-di-tert-butyl) Phenyl) octyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, G Lauryl trithiophosphite, bis (neopentyl glycol) 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl) -4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidene diphenyl phosphite, bis [2,2'-methylenebis (4 , 6-Diamylphenyl)]-isopropylidene diphenyl phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, tetratridecyl 4,4'-butylidenebis (2-tert-butyl-5- Methylphenol) diphosphite, hex (Tridecyl) • 1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane / triphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide, 2-butyl-2-ethylpropanediol, 2,4,6-tritert-butylphenol monophosphite, and the like.

  Examples of the phenol-based antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) -propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6 -Hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide] 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-methylenebis (4-methyl-6- Tributylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4, 4'-butylidenebis (6-tert-butyl-m-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6- Tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3) -Tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl)- 2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5- Ditert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5 .5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

  Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl, and distearyl, and β-alkyl mercapto of polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). Examples include propionic acid esters.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) benzotriazole, 2 -(2'-hydroxy-3 ', 5'-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5 Chlorobenzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy) such as-(2'-hydroxy-3'.5'-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol Phenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3 ′, 5′-ditertiarybutyl-4′-hydroxybenzoate, hexadecyl-3,5-ditertiarybutyl Benzoates such as -4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2′-ethoxyoxanilide and 2-ethoxy-4′-dodecyloxanilide; ethyl-α-cyano-β, β-diphenyl Acrylate, cyano such as methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate Acrylate compounds, and the like.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecyl succinimide, 1-[(3,5-ditert-butyl-4- Hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl- (3,5-ditert-butyl-4-hydroxyphenyl) propionate, bis (2,2,6,6- Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl- -Piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexa Methylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetra (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis ( 2,2,6,6-tetramethyl-4-piperidyl) .di (tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .di (tridecyl) butanetetra Carboxylate, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy] ) Butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2,6) , 6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,5,8,12-tetrakis [4,6 -Bis {N- (2,2,6,6-tetramethyl-4-piperidyl) butylamino} -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro-s-triazine / N, N '-Bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine / dibromoethane Examples include condensates.

  Examples of the inorganic metal compound include the metal species exemplified as the metal constituting the metal salt such as the organic carboxylic acid, for example, oxide, hydroxide, halide, perchlorate, carbonate, sulfate, nitrate. , Inorganic acid salts such as silicates and phosphates, and basic salts thereof.

  Examples of the composition of the present invention include calcium carbonate, silica, clay, glass beads, mica, sericite, glass flakes, asbestos, wollastonite, potassium titanate, PMF, gypsum fiber, zonotlite, MOS, and phosphate. Fillers such as fiber, glass fiber, carbon fiber, and aramid fiber; use pigments such as titanium oxide, petal, yellow lead, ultramarine, carbon black, azo pigment, phthalocyanine pigment, quinacridone pigment, dioxazine pigment Can do.

  Further, the composition of the present invention may include an impact resistance improver, a crosslinking agent, a foaming agent, an antistatic agent, an antifogging agent, a plate-out preventing agent, a surface treatment agent, a lubricant, a flame retardant, Light agents, fungicides, bactericides, metal deactivators, mold release agents, processing aids, and the like can be blended.

  Further, the composition of the present invention can be used regardless of the processing method of the vinyl chloride resin, for example, calendering, roll processing, extrusion molding, melt rolling, injection molding, pressurization. It can be suitably used for molding processing, paste processing, powder molding processing, foam molding processing and the like.

  The composition of the present invention comprises: wall materials, floor materials, window frames, wall materials, corrugated sheets, gutters, etc .; automotive interior and exterior materials; fish food packaging materials such as trays; packings, gaskets, hoses, pipes, Although it can be used as miscellaneous goods such as joints, sheets, and toys, it can be suitably used as a seat for automobiles.

  Examples The vinyl chloride resin composition of the present invention will now be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1
The following blend was blended with a Henschel mixer, and then roll kneaded under the conditions of 190 ° C. × 30 rpm × 0.6 mm × 5 minutes to prepare a sheet. The following sheet was subjected to the weather resistance test. The results are shown in Table 1 below.
(Composition) (Parts by mass)
Vinyl chloride resin 100
Pyromellitic acid tetra (C9-11 mixed alkyl ester) 72
Tricresyl phosphate 10
Epoxidized soybean oil 3
Barium-Zinc Liquid Stabilizer 2.5
Tetra (C12-15 mixed alkyl) -4,4′-iso 0.8
Propyridene diphenyl phosphite test compound (Table 1 listed) (Table 1 listed)

Weather resistance test: The obtained sheet was placed in a metal weather weather resistance tester (60 mW / cm ² , no shower, temperature: 63 ° C., humidity: 30% RH), and the yellowness after 60 hours was measured.

  Heat aging test: A prescribed test piece was prepared from the obtained sheet according to JIS K 7113, a tensile test was performed, and elongation (%) was measured. In addition, the urethane sheet on the obtained sheet was accelerated in deterioration at 120 ° C. for 500 hours, and then the urethane film was peeled off to prepare a test piece. A tensile test was performed to measure elongation (%). From the results, the residual elongation rate (elongation of the test piece after deterioration / elongation of the test piece before deterioration × 100,%) was determined.

※１：Ｍｇ_４Ａｌ_２（ＯＨ）_１２ＣＯ_３・３Ｈ_２Ｏの６０モル％過塩素酸処理品
※２：Ｍｇ_４Ａｌ_２（ＯＨ）_１２ＣＯ_３・３Ｈ_２Ｏの８０モル％過塩素酸処理品
※３：ビス（２，２，６，６−テトラメチル−４−ピペリジル）・ジ（トリデシル）ブタンテトラカルボキシレート
※４：ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）・ジ（トリデシル）ブタンテトラカルボキシレート

_{※ 1: Mg 4 Al 2 (} OH) 12 CO 3 · 3H 2 O 60 mole% perchloric acid treated product _{※ 2: Mg 4 Al 2 (} OH) 12 CO 3 · 3H 2 O 80 mole% perchloric acid Processed product * 3: Bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate * 4: Bis (1,2,2,6,6-pentamethyl-4- Piperidyl) ・ di (tridecyl) butanetetracarboxylate

Example 2
A vinyl chloride resin composition having the following composition was dried up at 130 ° C. for 2 hours in a gear oven, and then stirred for 15 minutes using a raker to prepare a compound. The chromium mirror plate is put out in a gear oven at 300 ° C. for about 15 minutes and then taken out. When the mirror plate reaches 240 ° C., the compound is quickly spread to a uniform thickness and left for 10 seconds. The mold was turned upside down and left as it was for 30 seconds, then immersed in a water bath and cooled to prepare a sheet.

(Composition) (Parts by mass)
Suspension polymerization vinyl chloride resin 90
Paste vinyl chloride resin 10
Trimellitic acid triester 80
Epoxidized soybean oil 3
12-hydroxystearic acid oligomer 0.2
Ivory pigment 5
Magnesium-zinc powder stabilizer 2.8
Tetra (C12-15 mixed alkyl) -4,4'-iso 0.5
Propyridene diphenyl phosphite test compound (Table 2 listed) (Table 2 listed)

  Weather resistance test: The obtained sheet was placed in a 83 ° C. fade meter to measure the burning occurrence time. The results are shown in Table 2 below.

※３および４は上記に同じ

* 3 and 4 are the same as above

  As is clear from the above examples, when a hindered amine compound having a specific carbonate skeleton was used alone (Comparative Example 1-1), it was inferior in heat-resistant aging properties, and perchlorate was used alone. (Comparative Example 1-2, Comparative Example 2-1) are inferior in weather resistance, and even when a hindered amine compound and a perchlorate are combined, the specific carbonate skeleton of the present invention is used. When a different compound from the hindered amine compound is used (Comparative Examples 1-3, 1-4, 2-2, 2-3), the effect of improving weather resistance is small.

  On the other hand, when a hindered amine compound having a specific carbonate skeleton and perchlorates were combined (Examples 1-1 to 1-5, 2-1), the heat-resistant physical properties were excellent and the weather resistance was remarkably improved. A resin composition was obtained.

Claims (5)

In 100 parts by mass of vinyl chloride resin, (a) the following general formula (I),

(In the formula, R represents an alkyl or hydroxyalkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, n represents an integer of 1 to 6, and when n = 1, R ¹ is An alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or the following general formula (III),

(R represents the same alkyl group having 1 to 30 carbon atoms or hydroxyalkyl group as that of R, or an alkenyl group having 2 to 30 carbon atoms), and when n = 2 to 6, R ¹ is n Represents an organic group having 2 to 20 carbon atoms)
Or the following formula (II),

(In the formula, R represents an alkyl group having 1 to 30 carbon atoms or a hydroxyalkyl group, or an alkenyl group having 2 to 30 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or carbon. Represents an alkenyl group having 2 to 22 atoms, A represents a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or an alkylene group having an ether bond, and n represents an integer of 2 to 6 , X is a linear or branched alkylene group having 4 to 40 carbon atoms having —C (═O) — or —C (═O) O— as a terminal, and having —C (═O) O— as a terminal. And a linear or branched alkylene group having 4 to 40 carbon atoms having an ether bond, a linear or branched alkylene group having 4 to 40 carbon atoms having a carbonic ester bond, or 3 to 6- O-C (= O)-end 0.001 to 10 parts by mass of at least one kind of hindered amine compound represented by an organic group having 6 to 30 carbon atoms at the end)
(B) 0.001 to 10 parts by mass of at least one selected from the group consisting of metal salts of perchloric acid, ammonium salts of perchloric acid, perchloric acid-treated hydrotalcite and perchloric acid-treated silicate, A vinyl chloride resin composition characterized by containing. The vinyl chloride resin composition according to claim 1, wherein, in the general formula (I), R is an alkyl group having 4 to 22 carbon atoms, n is 2, and R ¹ is an alkylene group having 2 to 12 carbon atoms. 2. The vinyl chloride according to claim 1, wherein in the general formula (I), n is 1 and R ¹ is a group of the general formula (III) (wherein R is an alkyl group having 10 to 22 carbon atoms). -Based resin composition.   4. The vinyl chloride resin composition according to claim 1, wherein the vinyl chloride resin composition is used for powder molding.   The vinyl chloride resin composition according to claim 1, which is used for an automobile sheet.